The present invention relates to iron particles for purifying a contaminated soil or ground water, a process for producing the iron particles, a purifying agent comprising the iron particles, a process for producing the purifying agent, and a method of purifying the contaminated soil or ground water. More particularly, the present invention relates to iron particles for purifying a soil or ground water contaminated with harmful substances such as organohalogen compounds, heavy metals, cyanogens and/or agricultural chemicals, which are capable of decomposing or insolibilizing the harmful substances contained in the soil or ground water, e.g., aliphatic organohalogen compounds such as dichloromethane, carbon tetrachloride, 1,2-dichloroethane, 1,1-dichloroethane, cis-1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, trichloroethylene, tetrachloroethylene and 1,3-dichloropropene, aromatic organohalogen compounds such as dioxins and PCB and/or heavy metals such as cadmium, lead, chromium (VI), arsenic and selenium as well as cyanogen or the like, in an efficient, continuous and economical manners; a process for producing the iron particle; a purifying agent comprising the iron particles; a process for producing the purifying agent; and a method of purifying the soil or ground water contaminated with the harmful substances such as organohalogen compounds, heavy metals, cyanogens and/or agricultural chemicals.
In the present invention, the “purifying” used herein means that in case of organohalogen compounds as harmful substances, the organohalogen compounds contained in a soil or ground water are decomposed, thereby purifying a soil or ground water contaminated with the organohalogen compounds, or in case of heavy metals or cyanogens as harmful substances, the heavy metals or cyanogens contained in a soil or ground water are insolubilized, thereby purifying a soil or ground water contaminated with the heavy metals or cyanogens. Further, in the present invention, the “purifying agent” used herein means an agent which decompose the organohalogen compounds contained in a soil or ground water, or insolubilize the heavy metals or cyanogens contained in a soil or ground water.
Aliphatic organohalogen compounds such as trichloroethylene, tetrachloroethylene or the like have been extensively used for cleaning in semiconductor factories and for degreasing metals to be machined.
Also, waste gases, fly ashes or main ashes discharged from an incineration furnace for combusting municipal garbage or industrial wastes, contain dioxins as aromatic organohalogen compounds having an extremely high toxicity to human bodies though the amount thereof is trace. The “dioxins” are a generic name of compounds obtained by substituting hydrogen atoms of dibenzo-p-dioxine, dibenzofuran, etc., with chlorine atoms. The waste gases or fly ashes continuously stay around the incineration furnace, resulting in residual of dioxins in soil of surrounding regions.
In addition, PCB (polychlorinated biphenyl) had been used in many application as insulating oils, plasticizers or heating medium for transformers, capacitors, etc., because of high chemical stability, thermal stability and excellent electrical insulating property thereof. Since the PCB is very harmful, the production and use thereof has been presently prohibited. However, any effective method of treating PCB past used has not been established until now and, therefore, a large part thereof has still been stored without treatment or disposal.
The above-described aliphatic organohalogen compounds and aromatic organohalogen compounds are hardly decomposable, and further exhibit carcinogenesis as well as a strong toxicity. Therefore, there arises such a significant environmental pollution that soil or ground water is contaminated with these organohalogen compounds.
More specifically, upon discharge of such organohalogen compounds, the aromatic organohalogen compounds such as dioxins and PCB which are hardly decomposable and exhibit a strong toxicity, cause significant environmental problems such as contamination of soil and ground water. In the case where such hardly-decomposable aromatic halogen compounds are accumulated in soil, the soil is contaminated therewith and as a result, the contaminated soil then cause contamination of ground water by the organohalogen compounds. Further, the contaminated ground water runs out from the contaminated soil to surrounding regions, so that pollution by the organohalogen compounds expands over much wider areas.
The land in which soil is once contaminated with the organohalogen compounds, cannot be reused and developed again. Therefore, there have been proposed various techniques or methods of purifying the soil and ground water contaminated with the organohalogen compounds. However, since the organohalogen compounds are hardly decomposable and a large amount of soil and ground water must be purified, any efficient and economical purifying techniques or methods cannot be fully established until now.
Alternatively, the contamination of soil or ground water by another harmful substances including heavy metals such as cadmium, lead, chromium (VI) and arsenic as well as cyanogen, etc., adversely affects human bodies and ecosystem. Therefore, the purification and removal of the above harmful substances have been urgently required.
As the method of purifying soil contaminated with the organohalogen compounds, there are known a purifying method using various catalysts; a method of absorbing and removing vapors of the organohalogen compounds by a volatility thereof; a thermal decomposition method of heat-treating excavated soil to render the soil harmless; a method of purifying soil by microorganism; or the like. In addition, as the method of purifying ground water contaminated with the organohalogen compounds, there are known a method of extracting the contaminated ground water from soil to treat the ground water into harmless one; a method of pumping the contaminated ground water to remove the organohalogen compounds therefrom; or the like.
Among these conventional methods of purifying soil or ground water contaminated with the organohalogen compounds, there have been proposed many methods of purifying soil or ground water contaminated with the organohalogen compounds into harmless ones by mixing and contacting the soil or ground water with a purifying agent composed of iron-based particles. Also, there are known methods of decomposing and removing the organohalogen compounds using iron-based particles such as mill scale, granular iron and sponge iron particles produced in iron and steel-making industries (Japanese Patent Application Laid-Open (KOKAI) Nos. 10-71386(1998), 11-235577(1999), 11-253908(1999), 2000-5740, 2000-225385, 2000-237768, 2000-334063, 2001-38341, 2001-113261, 2001-198567 and 2002-161263).
Here, general iron and steel-making processes are described.
The iron and steel-making processes are generally classified into an indirect process of first reducing iron ore into molten pig iron and then oxidation-refining the pig iron into steel, and a direct process of directly converting iron ore into steel through no production of pig iron.
In the pig iron production step of the indirect process (in which iron ore is reduced into pig iron), the iron ore together with lime stone (CaCO3) and coke are used as raw materials. The iron ore used in this process contains a gangue composed of hematite (mainly Fe2O3), magnetite (mainly Fe3O4), SiO2 and Al2O3 as main components. These raw materials are charged into a blast furnace where coke is burned by blowing a heated hot air thereto to produce a high-temperature mixed gas of CO and N2 by which the iron ore is reduced. The solid iron produced by the reduction reaction absorbs C while dropping downward in the blast furnace, and is melted into pig iron. Further, the molten pig iron absorbs C, Si, Mn, etc., to form a final composition. The pig iron is usually composed of 3.0 to 4.5% by weight of C, 0.2 to 2.5% by weight of Si, 0.02 to 0.5% by weight of Mn, 0.01 to 0.5% by weight of P, and 0.01 to 0.5% by weight of S. The gangue in the iron ore and ashes in the coke are chemically reacted with lime stone to form molten slag which is then separated from the molten pig iron by the difference in specific gravity therebetween. The thus separated pig iron is subjected, if required, to hot metal process.
The hot metal process for the molten pig iron includes desulfurizing, dephosphorizing and desiliconizing treatments. As the desulfurizing fluxes, there may be used CaO; CaF2, CaCl2 or the like. As the dephosphorizing fluxes, there may be used mill scale, iron ore or the like. Also, as the desiliconizing agent, there may be used iron oxide, manganese ore or the like.
Untreated molten pig iron or pig iron subjected to the hot metal process is then subjected to oxidation refining in a steel-making furnace using pure oxygen (steel-making step). Most of the steel-making furnaces are in the form of a composite converter. The steel-making furnace is charged with raw materials including the molten pig iron, scraps, and lime stone and fluorite as fluxes together with, if required, manganese ore. Upon supplying pure oxygen into the steel-making furnace, SiO2, FeO, CaO, CaF2, etc., are produced as slag, and then C is oxidized into CO (decarbonization), resulting in production of steel. Thereafter, the thus obtained steel is subjected, if required, to secondary refining process, and then, in most cases, formed into slab, bloom, billet, etc., by continuous casting process.
On the other hand, in the direct reduction process, iron ore, a reducing agent and a slag-forming agent are used as raw materials, and heat-treated in a crude iron-making furnace using fuel or electric heating to obtain solid granular iron or sponge iron through no production of pig iron. Then, the obtained solid iron is melted in an electric furnace, and subsequently cast into slab, bloom, billet, etc., by the same method as used in the indirect reduction process.
In any of the above-described processes, the iron compound produced in the steel-making step contains various impurities derived from the raw materials or additives. In particular, the inclusion of impurities becomes more remarkable in the steel-making step of the direct reduction process. In the case where soil or ground water contaminated with the organohalogen compounds are purified into harmless ones by mixing and contacting with a purifying agent composed of iron-based particles, in particular, in the case where the soil or ground water contaminated with the organohalogen compounds are treated using iron-based particles such as mill scale, granular iron or sponge iron particles produced in the steel-making step, attention must be paid to impurities remained in the iron-based particles.
In Japanese Patent Application Laid-Open (KOKAI) No. 10-71386(1998), there is described the method of drilling a bore in contaminated soil, blowing compressed air and iron particles into the bore to form a dispersion layer composed of the iron particles, and contacting the iron particles in the dispersion layer with the ground water to render harmful substances contained in the soil and ground water harmless. However, since detailed properties and specific amount of the iron particles used are not described, it is considered that this method fails to fully reduce the organohalogen compounds.
In Japanese Patent Application Laid-Open (KOKAI) No. 11-235577(1999), there is described the method of adding and mixing in soil, iron particles containing not less than 0.1% by weight of carbon, which are obtained by subjecting raw sponge ore-reduced iron particles to reduction-refining, sintering, pulverization and screening, to render organohalogen compounds contained in soil harmless. However, since the raw material used in this method is derived from iron ore, it is presumed that a large amount of impurities contained in most of common steel components or common cast iron components are involved therein. Therefore, the iron particles may fail to show a high purification property against the organohalogen compounds. In addition, although the specific surface area and particle size of the iron particles are described, since the particle size thereof is too large, it may be difficult to fully reduce the aromatic organohalogen compounds.
In Japanese Patent Application Laid-Open (KOKAI) No. 11-253908(1999), there is described the method of uniformly mixing PCB with metal particles and then heating the obtained uniformly kneaded material to form a metal chloride, thereby rendering the PCB harmless. However, in Examples of this KOKAI, it is essentially required to heat the kneaded material at a temperature of not less than 250° C. Therefore, this method may fail to provide an economical process.
In Japanese Patent Application Laid-Open (KOKAI) No. 2000-5740, there is described the method of rendering organohalogen compounds contained in soil harmless by using copper-containing iron particles. However, similarly to the iron particles described in Japanese Patent Application Laid-Open (KOKAI) No. 11-235577(1999), since the iron particles obtained by subjecting raw sponge ore-reduced iron particles to reduction-refining, sintering, pulverization and screening, are used as a raw material, i.e., the raw material is derived from iron ore, it is presumed that a large amount of impurities contained in most of common steel components or common cast iron components are still contained therein. Therefore, the iron particles may fail to show a high purification property against the organohalogen compounds. Further, since decomposition of the organohalogen compounds requires a long period of time, this method may fail to efficiently convert the organohalogen compounds into harmless ones.
In Japanese Patent Application Laid-Open (KOKAI) No. 2000-225385, there is described the method of subjecting halogenated hydrocarbons to reduction-dehalogenation by chemically reacting the halogenated hydrocarbons with a reducing metal in the presence of a hydrogen donating compound. However, since this method essentially requires to use amines for accelerating the dehalogenation reaction, it is difficult to fully conduct the decomposition reaction by the reducing metal.
In Japanese Patent Application Laid-Open (KOKAI) No. 2000-237768, there is described the method of contacting organohalogen compounds with iron-based metals. However, since the iron-based metals are in the form of fibers having a large fiber diameter, this method may also fail to fully reduce the aromatic organohalogen compounds.
In Japanese Patent Application Laid-Open (KOKAI) No. 2000-334063, there is described the method of contacting dioxins with an aqueous hydrochloric acid solution containing mill scale produced in the production process of hot-rolled steel plate in ironworks, at a temperature lower than 100° C. to render the dioxins harmless. However, it is presumed that the mill scale itself contains impurities such as Mn, Si, Cr, Al, P and Ca in an amount of from several hundreds ppm to several thousands ppm. Therefore, the mill scale may fail to show a high purification property against the organohalogen compounds. Also, in order to promote conversion of the organohalogen compounds into harmless ones, since the use of the aqueous hydrochloric acid solution is essentially required, the mill scale by itself may fail to sufficiently promote the decomposition reaction.
In Japanese Patent Application Laid-Open (KOKAI) No. 2001-38341, there is described a soil-purifying agent composed of a water suspension containing iron particles having an average particle diameter of 1 to 500 μm. However, since the iron particles used have a too large particle size, it may be difficult to fully decompose the organohalogen compounds.
In Japanese Patent Application Laid-Open (KOKAI) No. 2001-113261, there is described the method of contacting dioxin-contaminated soil with an aqueous hydrochloric acid solution containing an iron compound to render the dioxins harmless. However, in order to promote the conversion of dioxins into harmless ones, since the use of the aqueous hydrochloric acid solution is essentially required, the iron compound by itself may fail to sufficiently promote the decomposition reaction.
In Japanese Patent Application Laid-Open (KOKAI) No. 2001-198567, there is described the purification method using a water suspension containing spherical iron particles having an average particle diameter of less than 10 μm. The spherical iron particles contained in the water suspension are obtained by collecting dusts contained in waste gas discharged during refining process from an oxygen blowing converter for steel-making where pig iron containing C, Si, P, etc., is oxidation-refined by blowing oxygen thereinto, and removing gases from the dusts. However, it is presumed that the thus obtained spherical iron particles contain impurities such as C, Si and P in the form of oxides. Therefore, the spherical iron particles may fail to show a high purification property against the organohalogen compounds. Further, since the water suspension containing the spherical iron particles obtained by collecting dusts contained in waste gas discharged during refining process from an oxygen-blowing converter for steel-making and removing gases from the dusts, the iron particles have a broad particle size distribution and, therefore, exhibit a non-uniform penetration velocity into contaminated soil, resulting in delayed purification performance and prolonged purification time. For this reason, the water suspension may also fail to fully reduce the organohalogen compounds. In addition, although spherical iron particles having an average particle diameter of 1.3 μm were used in Examples of this KOKAI, since the metal iron content thereof is low, it may be difficult to fully reduce the organohalogen compounds.
In Japanese Patent Application Laid-Open (KOKAI) No. 2002-161263, there are described iron particles for decomposing organohalogen compounds, in which a part of the surface of the iron particles is adhered with at least one metal selected from the group consisting of nickel, copper, cobalt and molybdenum, and the remaining surface other than the surface adhered with the above metal is covered with an iron oxide layer. However, the iron particles used are either iron particles obtained by subjecting sponge iron particles obtained by reducing mill scale discharged from the production process of hot-rolled steel plate, etc., in ironworks by using coke, to finish-reduction treatment under a hydrogen flow, or iron particles obtained by atomizing molten steel with water. For this reason, since it is presumed that the iron particles usually contain a large amount of impurities derived from the mill scale or molten steel, the iron particles may fail to show a high purification property against the organohalogen compounds. Further, as is apparent from the specific surface area of the iron particles as described therein, it is considered that the iron particles have a large particle size. Thus, the iron particles may also fail to fully reduce the organohalogen compounds.
On the other hand, the other harmful substances contained in contaminated soil or ground water including heavy metals such as cadmium, lead, chromium (VI) and arsenic as well as cyanogen, agricultural chemicals or the like, are similarly harmful to human bodies and ecosystem. Therefore, the development of methods for purification and removal of these harmful substances has also been demanded.
As known in the art, technical means for treatment of soil or ground water contaminated with harmful substances such as heavy metals, cyanogen, agricultural chemicals, etc., are classified into two categories, i.e., “purification techniques” and “containment”. Further, the purification techniques are classified into “in-situ purification” and “removal by excavation” for excavating and removing contaminated soil from objective land. Furthermore, the “in-situ purification” techniques are classified into “in-situ decomposition” in which heavy metals, cyanogen, agricultural chemicals, etc., contained in contaminated soil or ground water, are decomposed under the ground (in situ), and “in-situ extraction” in which contaminated soil or ground water is extracted or excavated, and then heavy metals, cyanogen, agricultural chemicals, etc., contained in the soil or ground water are removed therefrom.
Further, the “in-situ extraction” techniques are classified into “decomposition” in which compounds such as cyanogen, agricultural chemicals, etc., among objective substances, are thermochemically decomposed, and “separation” in which concentrated heavy metals are physically separated from the contaminated soil or ground water.
On the other hand, the “containment” techniques are classified into “in-situ containment” and “containment after removal by excavation”. The in-situ containment techniques are techniques of solidifying contaminated soil by mixing a solidifying agent therewith, and then confining the contaminated soil in situ without removal therefrom. The techniques of containment after removal by excavation are techniques of pre-mixing an insolubilizing agent with contaminated soil to render the soil hardly soluble, drilling the contaminated soil and then confining the contaminated soil in another place.
As the working methods for performing the “purification techniques”, there may be used a soil-washing method, a heat-desorption method or the like. For example, there may be used a chemical dissolution method of adding chemicals to contaminated soil or the like to dissolve heavy metals, etc., and then separating the obtained solution therefrom; a water-washing method of washing contaminated soil with water and then classifying the soil to separate fine particles containing a large amount of heavy metals therefrom; a wet soil-washing method of washing out contaminants adhered onto the surface of soil particles with a washing agent, and further classifying the soil particles into clean large particles and contaminated fine particles according to particle size and specific gravity thereof; or the like.
Also, in the “containment” techniques, as the working method for the “in-situ containment”, there may be used a method of mixing a solidifying agent such as cement with contaminated soil and then confining the solidified soil by a water-impermeable layer, steel sheet pile, etc. As the working method for the “containment after removal by excavation”, there may be used a method of adding chemicals to contaminated soil to change the soil into insolubilized form, and then confining the elution-free soil by insulating or water-shielding method.
However, the above conventional treatment techniques undergo high treating costs, and require a long treating time. Therefore, these techniques may fail to reduce harmful substances such as heavy metals, cyanogen, agricultural chemicals, etc., in efficient and continuous manners.
To solve the above problems, there have been developed low-cost treating techniques of decreasing a valence of the heavy metals mainly by a reducing activity of iron particles in order to convert the metals into harmless and stabilized form. For example, there are known techniques using a reducing activity of iron particles (decrease in valence of metals) (Japanese Patent Application Laid-Open (KOKAI) No. 10-71386(1998)); techniques using a reducing activity or adsorptivity of iron particles to arsenic (Japanese Patent Application Laid-Open (KOKAI) No. 10-244248(1998)); techniques using heat-treatment in combination with a reducing activity of iron particles (decrease in valence of metals) (Japanese Patent Application Laid-Open (KOKAI) No. 2000-157961); techniques using a reducing activity of iron particles (decrease in valence of metals) to chromium (VI) (Japanese Patent Application Laid-Open (KOKAI) No. 2001-198567); techniques using a reducing activity of iron particles (decrease in valence of metals) (Japanese Patent Application Laid-Open (KOKAI) No. 2002-200478); or the like.
The above-described techniques are directed to methods of converting contaminants such as heavy metals into harmless and stabilized form by using the reducing activity of iron particles (decrease in valence of metals). Therefore, with the passage of years, there arise problems such as deterioration in persistency of reducing activity of the iron particles. As a result, there is such a tendency that the heavy metals converted into harmless and stabilized ones having a low valence, are converted again into harmful metals having an increased valence. Thus, the above techniques may fail to provide a method or measure that is effectively usable for a long period of time.
In addition, as the method for treating heavy metal-containing waste water, there have been proposed a ferrite-formation method of treating the waste water by adding an iron salt thereto, and a method of stabilizing the heavy metals due to reducing activity of iron particles.
The ferrite-formation method is a method of neutralizing Fe2+ or Fe3+ with alkali, and oxidizing the neutralized Fe into spinel ferrite by passing air therethrough or by using an oxidizing agent under heating (or at ordinary temperature), thereby allowing heavy metals to be incorporated or adsorbed into crystals of the thus formed spinel ferrite. It is also known that some heavy metals are incorporated or adsorbed into crystals of iron oxide hydroxide such as α, γ or δ-FeOOH (“Treatment of heavy metal-containing waste water by ferrite method” in “NEC Technical Report”, Vol. 37, No. 9/1984; and Japanese Patent Application Laid-Open (KOKAI) Nos. 50-36370(1975), 50-133654(1975) and 50-154164(1975)).
The method of stabilizing the heavy metals due to reducing activity of iron particles is a method of reducing a valence of the heavy metals to convert the metals into harmless and stabilized form. Meanwhile, it is also known that some heavy metals are incorporated or adsorbed into crystals of goethite or spinel ferrite formed by dissolution of a small amount of iron particles in an acid region.
For example, in Japanese Patent Publication (KOKOKU) No. 52-45665(1977), it is described that upon adding iron particles to a heavy metal ion-containing solution whose pH value is adjusted to about 5 to 6, and stirring the resultant mixture, a part of the iron particles is dissolved and precipitated as ferric hydroxide which is then converted into goethite or lepidocrocite with the increase of pH value, whereupon a part of the heavy metals is co-precipitated with the goethite or lepidocrocite, and a large part of the heavy metals is adsorbed into the iron particles. Also, it is described that when the pH value is low, elution of the iron particles is increased, resulting in deterioration in the adsorption/removal effect thereof.
In Japanese Patent Publication (KOKOKU) No. 54-11614(1979), it is described that when iron particles are added to a heavy metal chelate complex-containing solution whose pH value is adjusted to 2 to 6, and the resultant mixture is reacted under such a strong stirring as to entangle air therein or by blowing air thereinto under stirring to naturally increase the pH value of the solution, the surface of the iron particles is activated to adsorb the heavy metals thereonto. Also, it is described that a part of the iron particles are converted into goethite, lepidocrocite or magnetite, and the heavy metals are incorporated into crystals thereof.
In Japanese Patent Application Laid-Open (KOKAI) No. 57-7795(1982), it is described that iron particles are added to an iron cyanide complex-containing solution whose pH value is adjusted to less than 5, and the resultant mixture is stirred, thereby dissolving a part of the iron particles and allowing the iron cyanide complex to be adsorbed into iron. In addition, there are also described various reactions such as reduction reaction (decrease in valence of metals), substitution precipitation (ionization tendency), adsorption reaction onto iron particles, incorporation by formation of iron oxide, precipitation of hydroxides by neutralization, and co-precipitation reaction (ferrite formation).
In any of the above-described conventional techniques, the iron particles mainly exhibit either reduction activity or adsorptivity. Although some of the conventional techniques describe the dissolution effect of the iron particles, almost all of the conventional techniques relate to a mechanism in which the iron particles are converted via elution thereof in an acid region into goethite, lepidocrocite or magnetite to incorporate heavy metals into crystals thereof. The mechanism is, however, different from techniques based on such a phenomenon that upon treatments using iron particles, Fe2+ or Fe3+ is dissolved and formed into spinel ferrite while incorporating heavy metals thereinto.
In “Air Oxidation of Iron Powder Dispersed in Aqueous Solution of Sodium Hydroxide”, Bull. Inst. Chem. Res. Kyoto Univ., Vol. 71, No. 2(1993), it is described that a spinel compound is produced from iron particles through dissolution thereof. However, this technique essentially requires pH adjustment by addition of alkali as well as heating and forced oxidation.
As a result of the present inventors' earnest studies for solving the above problems, it has been found that by mixing and contacting with soil or ground water containing harmful substances such as organohalogen compounds and/or heavy metals, cyanogen, etc., and iron particles obtained by heat-reducing goethite particles having an average major axis diameter of 0.05 to 0.50 μm or hematite particles obtained by heat-dehydrating the goethite particles at a temperature of 250 to 350° C., at a temperature of 250 to 600° C., thereby producing iron particles, after cooling, (i) transferring the iron particles into water without forming a surface oxidation film on surface of the iron particles in a gas phase, forming the surface oxidation film on the surface of the iron particles in water; and then drying the iron particles, or (ii) forming the surface oxidation film on the surface of the iron particles in a gas phase, it is possible to treat the harmful substances such as organohalogen compounds and/or heavy metals, cyanogen, etc. contained in the soil or ground water in efficient, continuous and economical manners. The present invention has been attained on the basis of this finding.